Glass-reinforced branched higher alpha-olefin polymers

ABSTRACT

Compositions of stabilized stereoregular polymers of branched higher alpha-olefins, grafting compounds, free radical generators, glass and epoxy resins and/or epoxy-functional silanes and/or hydroxy functional compounds are provided as well as methods for making these compounds and articles thereof.

This application is a divisional application of Ser. No. 08/182,881,filed Jan. 18, 1994, which is a divisional application of Ser. No.07/967,300, filed Oct. 26, 1992, now U.S. Pat. No. 5,308,893, which is acontinuation-in-part application of Ser. No. 07/674,646, filed Mar. 22,1991, abandoned.

FIELD OF THE INVENTION

This invention relates to glass-reinforced branched higheralpha-olefins.

BACKGROUND OF THE INVENTION

Polyolefins tend to have excellent physical and chemical properties.Improvement of polymer properties is a dominant factor in thedevelopment and production of olefin polymers. Several methods have beenemployed to improve various polymer properties. The prior art teachesthat reinforcing agents, such as glass fibers, can be incorporated intothe polymer to improve the mechanical properties and/or the heatresistance of the polymer. However, merely mixing the glass fibers andthe polyolefins together can result in weak bonding between the glassfibers and the polyolefin. One solution is to have a more bondablecomponent grafted onto the polymers to facilitate reinforcement withglass fibers and other generally infusible reinforcing agents.

Polymers with relatively high melting points, such as stereoregularpolymers of branched, higher alpha-olefins, have been developed. Thesepolymers are useful in high temperature applications, such as microwavepackaging. Improving the performance and/or properties of these polymerscould expand the variety of uses of these polymers.

Polymers of branched higher alpha-olefins have been modified withgrafting reactions to incorporate functional chemical moieties toimprove the adhesion between the alpha-olefin matrix and the glassreinforcement as has been disclosed in U.S. Pat. No. 4,888,394, Dec. 19,1989.

Glass fiber reinforcement products are usually sized either during thefiber formation process or in a posttreatment. Sizing compositions foruse in treating glass fibers usually contain a lubricant, which providesthe protection for the glass fiber strand; a film-former or binder thatgives the glass fiber strand integrity and workability; a coupling agentthat provides better adhesion between the glass fiber strand and thepolymeric materials that are reinforced with the glass fiber strand; andother additives such as emulsifiers, wetting agents, nucleating agents,and the like. Various sizing compositions have been developed for glassfiber reinforcements to provide improved adhesion between variouspolymeric materials and the glass fiber. Sizing compositions are knownfor treating glass fibers for improved adhesion between the glass fiberstrand and relatively low melting point polyolefins, such aspolyethylene and polypropylene. The polyolefin may be modified partiallyor entirely with an unsaturated carboxylic acid or derivative thereof.The prior art does not teach sizing compositions for treating glassfibers for improved adhesion between glass fibers and stereoregularpolymers of branched higher alpha-olefins or stereoregular polymers ofbranched higher alpha-olefins which have been modified with unsaturatedsilanes, carboxylic acids, or derivatives thereof.

SUMMARY OF THE INVENTION

It is an object of this invention to provide glass-reinforced branchedhigher alpha-olefins with improved adhesion between the higheralpha-olefin matrix and the glass reinforcement.

It is another object of this invention to provide methods for makingglass-reinforced branched higher alpha-olefins with improved adhesionbetween the higher alpha-olefin matrix and the glass reinforcement.

It is an object of this invention to provide glass-reinforcedthermoplastic materials from which products with improved properties canbe made.

It is another object of this invention to provide methods for makingglass-reinforced thermoplastic materials from which products withimproved properties can be made.

In one embodiment of this invention a composition comprises:

(a) a stereoregular polymer of branched higher alpha-olefins which hasbeen stabilized with at least one hindered phenol;

(b) a grafting compound selected from the group consisting ofvinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylicacids; carboxylic acid derivatives; carboxylic acid anhydrides;carboxylic acid anhydride derivatives; and mixtures thereof;

(c) a free radical generator;

(d) glass; and

(e) at least one epoxy resin.

Another embodiment of this invention is a composition comprising:

(a) a stereoregular polymer of branched higher alpha-olefins which hasbeen stabilized with at least one hindered phenol;

(b) a grafting compound selected from the group consisting ofvinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylicacids; carboxylic acid derivatives; carboxylic acid anhydrides;carboxylic acid anhydride derivatives; and mixtures thereof;

(c) a free radical generator;

(d) glass; and

(e) at least one epoxy-functional silane.

In yet another embodiment of this invention a composition comprises:

(a) a stereoregular polymer of branched higher alpha-olefins which hasbeen stabilized with at least one hindered phenol;

(b) a grafting compound selected from the group consisting ofvinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylicacids; carboxylic acid derivatives; carboxylic acid anhydrides;carboxylic acid anhydride derivatives; and mixtures thereof;

(c) a free radical generator;

(d) glass;

(e) at least one epoxy resin; and

(f) at least one epoxy-functional silane.

Any of the three foregoing embodiments of this invention may optionallycontain hydroxy-functional compounds.

In accordance with this invention methods are provided for making thecompositions of this invention.

Also in accordance with this invention articles made from thecompositions of the invention are provided.

DETAILED DESCRIPTION OF THE INVENTION

The mechanical and thermal properties and property retentioncharacteristics of stereoregular polymers of branched higheralpha-olefins are improved by compounding with glass fibers. Thesepolymers are further improved by chemical coupling of the polymer matrixto the glass reinforcing fibers. The resultant compounds have excellentelectrical properties, high strength, and good thermal and chemicalresistance, which are beneficial in a variety of automotive andelectrical applications. For example, products made with theglass-reinforced polymers of this invention have exhibited significantlyhigher heat deflection temperatures than products made with otherglass-reinforced polymers.

Surprisingly excellent mechanical and thermal properties can be obtainedby (a) modifying stabilized, stereoregular polymers of branched higheralpha-olefin polymers with unsaturated silanes, carboxylic acids, and/orcarboxylic acid anhydrides in the presence of a free radical generatorin the polymer melt, and then (b) reinforcing these modified polymerswith glass which has been sized with compositions which contain at leastone epoxy resin or at least one epoxy-functional silane or both at leastone epoxy resin and at least one epoxy-functional silane. It has alsobeen discovered that further unexpected improvements in properties canbe obtained by (c) adding hydroxy-functional compounds to the inventivecompositions.

Polymers

Polymers considered suitable for use in this invention are olefinicpolymers which have a melting point higher than about 180° C., morepreferably, a melting point of greater than about 190° C. Polymersproduced from linear monomers, such as ethylene, propylene, butene, andhexene, usually have lower melting points than polymers of branchedhigher alpha-olefins. Thus, the polymers useful in this invention arehomopolymers and copolymers of branched higher alpha-olefins. Thepreferred alpha-olefin monomers have from about 4 to 12 carbon atoms.Exemplary monomers include, but are not limited to, 3-methyl-1-butene(3MB1), 3-methyl-1-pentene (3MP1), 4-methyl-1-pentene (4MP1),4-methyl-l-hexene (4MH1), 3,3-dimethyl-1-butene (3,3DMB1),4,4-dimethyl-1-hexene (4,4DMH1), 3-ethyl-1-hexene (3EH1) and othersimilar monomers. Most preferably, polymers of 4MP1, also calledpolymethylpentene (PMP), and 3MB1, also called polymethylbutene (PMB),are utilized in this invention. Table I gives the approximate meltingpoint of each homopolymer listed above.

                  TABLE I    ______________________________________    Melting Points of Some of the Polymers    Useful in this Invention                     Approximate                     Melting    Polymerized Monomer                     Temperature, °C.    ______________________________________    3-methyl-1-butene                     300    3-methyl-1-pentene                     370    4-methyl-1-pentene                     240    4-methyl-1-hexene                     196    3-ethyl-1-hexene 425    3,3-dimethyl-1-butene                     400    4,4-dimethyl-1-hexene                     350    ______________________________________

The term "polymer", as used in this disclosure, includes homopolymers,as well as copolymers. Copolymers comprise the product resulting fromcombining a branched higher alpha-olefin with any other olefin monomeror monomers. For example, a branched higher alpha-olefin can bepolymerized in the presence of, or in series with, one or more olefinmonomers. Generally, applicable comonomers have from about 2 to about 18carbon atoms and preferably, have from about 8 to about 16 carbon atoms.Most preferably, the comonomer or comonomers are linear alpha-olefins.Longer chain linear olefins are preferred in that they are easier tocopolymerize with branched higher alpha-olefins and can impart increasedclarity, stability, and impact strength to the resultant polymer.Exemplary comonomers include, but are not limited to, 1-octene,1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and other higherolefins. A polymer can also be obtained by physically blendinghomopolymers and/or copolymers.

In general, it is preferred for the polymer to comprise at least about85 mole percent moieties derived from branched higher alpha-olefins, andmore preferably, at least about 90 mole percent moieties derived frombranched higher alpha-olefins. Most preferably, the polymer comprises atleast about 95 mole percent moieties derived from branched higheralpha-olefins, which results in a polymer of superior strength and ahigh melting point.

Polymer Stabilizing Package

After the polymer has been produced, it is essential, according to thisinvention, that the polymer be given a prophylatic charge with ahindered phenol before additional processing of the polymer. Thehindered phenol acts as an antioxidant and improves the heat, light,and/or oxidation stability of the polymer. As a result of theprophylactic charge, the polymer product can withstand drying andstorage after the polymerization process. Any hindered phenol in anamount which improves the heat, light, and/or oxidation stability of thepolymer is applicable. Exemplary hindered phenol compounds include, butare not limited to, 2,6-di-tert-butyl-4-methylphenol; tetrakis(methylene3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)methane; thiodiethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate); octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate;1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate;1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene;and/or 2,2'-methylene bis(4-methyl-6-tert-butylphenol). Preferably thehindered phenol antioxidant used for the prophylactic charge is selectedfrom the group consisting of 2,6-di-tert-butyl-4-methylphenol;tetrakis(methylene3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)methane; octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; and mixtures thereofbecause of ease of use, availability, and economic reasons.

In addition to the essential prophylactic charge of hindered phenol,other antioxidants or stabilizers can be added to further stabilize thepolymer. The type(s) of stabilizer(s) used depends on the finalapplication or use of the polymer. Numerous polymer additives arecommercially available and are usually selected from the groupconsisting of additional hindered phenols, organic phosphites, hinderedamine light stabilizers, thioesters, aliphatic thio compounds andmixtures thereof.

The total polymer stabilizer package that can be added prior tografting, which comprises the essential hindered phenol antioxidantprophylactic charge, and the optional additional hindered phenol,organic phosphite, thioesters and/or hindered amine light stabilizer, isusually added to the polymer in an amount in the range of about 0.05 toabout 2 parts by weight of total stabilizer(s) per 100 parts by weightof polymer (phr). Preferably, the hindered phenol prophylactic chargecomprises an amount in the range of about 0.1 to about 1 phr, and mostpreferably in an amount in the range of about 0.1 to about 0.8 phr. Ifinsufficient hindered phenol is present, oxidative degradation of thepolymer can occur. The presence of excess hindered phenol can interferewith the grafting process. If desired, additional stabilizers, i.e., inexcess of 2 phr, can be added any time alter the grafting process,depending upon the desired polymer properties.

Other Polymer Additives

Other additives can optionally be incorporated into the polymer, beforeand after grafting, to achieve additionally desired beneficial polymerproperties. General exemplary additives include, but are not limited to,antioxidants, antioxidant synergists, UV absorbers, nickel stabilizers,pigments, plasticizing agents, optical brighteners, antistatic agents,flame retardants, lubricating agents, metal inhibitors, and the like.Processing lubricams can also be added to enhance polymer properties.Examples of processing lubricants include, but are not limited to, fattyacids containing from about 10 to about 20 carbon atoms and the metalsalts thereof. Usually, metal stearates, such as, for example, calciumstearate and zinc stearate, and/or metal laurates are used as processinglubricants and/or acid scavengers for polyolefins. If corrosion is apotential problem, one or more corrosion inhibitors can be added.

Any additive can be combined with the polymer according to any methodknown in the art. Examples of incorporation methods include, but are notlimited to, dry mixing in the form of a powder and wet mixing in theform of a solution or slurry. In these types of methods, the polymer canbe in any form, such as, for example, fluff, powder, granulate, pellet,solution, slurry, and/or emulsion. For ease of operation, the initialprophylactic charge of hindered phenol is usually solution or slurrymixed with the polymer prior to drying and handling of the polymer. Anyadditional stabilizers or additives can be blended with the polymerprior to grafting, added to the polymer melt during the grafting orglass reinforcing process, and/or added during reprocessing of thegrafted, glass reinforced polymer.

Grafting Compounds

The stabilized, stereoregular polymers of branched higher alpha-olefinsare modified by grafting with a radically polymerizable unsaturatedgrafting compound selected from the group consisting ofvinyl-polymerizable, unsaturated, hydrolyzable silane compounds,carboxylic acids and derivatives, carboxylic acid anhydrides andderivatives, and mixtures thereof, in the presence of a free radicalgenerator.

The vinyl-polymerizable unsaturated, hydrolyzable silanes used in thisinvention contain at least one silicon-bonded hydrolyzable group, suchas, for example, alkoxy, halogen, and acryloxy, and at least onesilicon-bonded vinyl-polymerizable unsaturated group such as, forexample, vinyl, 3-methacryloxypropyl, alkenyl, 3-acryloxypropyl,6-acryloxyhexyl, alkynyloxypropyl, ethynyl, and 2-propynyl. Thesilicon-bonded vinyl-polymerizable unsaturated group preferably is anethylenically unsaturated group. Any remaining valances of silicon notsatisfied by a hydrolyzable group or a vinyl-polymerizable unsaturatedgroup are satisfied by a monovalent hydrocarbon group, such as, forexample, methyl, ethyl, propyl, isopropyl, butyl, pentyl, isobutyl,isopentyl, octyl, decyl, cyclohexyl, cyclopentyl, benzyl, phenyl,phenylethyl, and naphthyl. Suitable silanes of this type include thoserepresented by the formula:

    R.sub.a SiX.sub.y T.sub.c

wherein R is a monovalent hydrocarbon group, X is a silicon-bondedhydrolyzable group, Y is a silicon-bonded monovalent organic groupcontaining at least one vinyl-polymerizable unsaturated bond, a is aninteger of 0 to 2, preferably 0; b is an integer of 1 to 3, preferably3; c is an integer of 1 to 3, preferably 1; and a+b+c is equal to 4.

Suitable vinyl-polymerizable unsaturated hydrolyzable silanes that canbe used in this invention include, but are not limited to,3-acryloxypropyltriethoxysilane, ethynyltriethoxysilane,2-propynyltrichlorosilane, 3-acryloxypropyldimethylchlorosilane,3-acryloxypropyldimethylmethoxysilane,3-acryloxypropylmethyldichlorosilane, 3-acryloxypropyltrichlorosilane,3-acryloxypropyltrimethoxysilane, allyldimethylchlorosilane,allylmethyldichlorosilane, allyltrichlorosilane, allyltriethoxysilane,allyltrimethoxysilane, chloromethyldimethylvinylsilane,2-(3-cyclohexenyl)ethyl!dimethylchlorosilane,2-(3-cyclohexenyl)ethyltrimethoxysilane, 3-cyclohexenyltrichlorosilane,diphenylvinylchlorosilane, diphenylvinylethoxysilane,(5-hexenyl)dimethylchlorosilane, (5-hexenyl)diethylchlorosilane,5-hexenyltrichlorosilane, 3-methacryloxpropyldimethylchlorosilane,3-methacryloxypropyldimethylethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-methacryloxypropyltrichlorosilane,methyl-2-(3-cyclohexenyl)-ethyldichlorosilane,methyl-3-(trimethylsiloxy)crotonate, 7-octenyltrichlorosilane,7-octenyltrimethoxysilane, 1-phenyl-1-trimethylsiloxyethylene,phenylvinyldichlorosilane, styrylethyltrimethoxysilane,1,3-tetradecenyltrichlorosilane, 4- 2-(trichlorosilyl)ethyl!cyclohexene,2-(trimethylsiloxy)ethylmethacrylate, 3-(trimethylsilyl)cyclopentene,vinyldimethylchlorosilane, vinyldimethylethoxysilane,vinylethyldichlorosilane, vinylmethyldiacetoxysilane,vinylmethyldichlorosilane, vinylmethyldiethoxysilane,vinyltrimethylsilane, vinyltrichlorosilane, vinyltriethoxysilane,vinyltrimethoxysilane, vinyltris(beta-methoxyethoxy)silane,vinyltriacetoxysilane, 3-methacryloxypropyltdmethoxysilane,3-methacryloxypropyltris(beta-methoxyethoxy)silane and mixtures thereof.

The preferred silane compounds are vinyltrichlorosilane,vinyltriethoxysilane, vinyltrimethoxysilane,vinyltris(beta-methoxyethoxy)silane, vinyltriacetoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropyltris(beta-methoxyethoxy)silane, and mixturesthereof. These compounds are preferred due to commercial availability,ease of use, as well as good polymer property improvement.

The radically polymerizable unsaturated grafting compound also can be acarboxylic acid or an anhydride thereof, with about three to about 10carbon atoms, with preferably at least one olefinic unsaturation, andderivatives thereof. Examples of the carboxylic acid and anhydrideinclude, but are not limited to, an unsaturated monocarboxylic acid suchas acrylic acid or methacrylic acid; an unsaturated dicarboxylic acidsuch as maleic acid, fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, muconic acid (mesaconic acid), glutaconic acid,norbornene-2,3-dicarboxylic acid (tradename Nadic acid), methyl Nadicacid, tetrahydrophthalic acid, or methylhexahydrophthalic acid; anunsaturated dicarboxylic anhydride such as maleic anhydride, itaconicanhydride, citraconic anhydride, allyl succinic anhydride, glutaconicanhydride, Nadic anhydride (Trademark for norbornene-2,3-dicarboxylicanhydride), methyl Nadic anhydride, tetrahydrophthalic anhydride, ormethyltetrahydrophthalic anhydride; or a mixture of two or more thereof.Of these unsaturated carboxylic acids and acid anhydrides thereof,maleic acid, maleic anhydride, muconic acid, Nadic acid, methyl Nadicacid, methyl Nadic anhydride, or Nadic anhydride is preferably used.

The radically polymerizable unsaturated grafting compound is present inthe reaction mixture in an amount sufficient to improve the propertiesof the resultant grafted polymer. Usually, the amount is in the range ofabout 0.1 to about 2 parts of radically polymerizable unsaturatedgrafting compound per 100 parts of polymer (phr), preferably in therange of about 0.2 to about 1.6 phr, and most preferably in the range ofabout 0.4 to about 1.2 phr. If too much grafting compound is used, notall of the grafting compound will be grafted onto the polymer and noadditional appreciable polymer property improvement is obtained; anexcess is economically undesirable. Use of too little grafting compounddoes not improve or enhance the polymer properties. In general, thegrafting compounds used in this invention have similar amounts offunctionality.

The grafting reaction must occur in the presence of a free radicalgenerator, also called a free radical initiator. An organic peroxide ispreferably used as the free radical initiator in the graff modificationreaction as described above. More specifically, preferred examples of anorganic peroxide include, but are not limited to, alkyl peroxides, arylperoxides, acyl peroxides, aroyl peroxides, ketone peroxides,peroxycarbonates, peroxycarboxylates, hydroperoxides, and other organicperoxides. Examples of an alkyl peroxide include diisopropyl peroxide;di-tert-butyl peroxide; 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3;a,a'-bis(tert-butylperoxy)diisopropyl benzene; and2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane. An example of an arylperoxide is dicumyl peroxide. An example of an acyl peroxide isdilauroyl peroxide. An example of an aroyl peroxide is dibenzoylperoxide. Examples of a ketone peroxide include methyl ethyl ketoneperoxide and cyclohexanone peroxide. Examples of hydroperoxide includetert-butyl hydroperoxide and cumene hydroperoxide. Preferred examples ofa free radical initiator are di-tert-butyl peroxide;2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3;2,5-dimethyl-2,5-di(tert-butyl-peroxy)hexane, dicumyl peroxide;a,a'-bis(tertbutylperoxy)diisopropylbenzene; and mixtures thereof.Higher molecular weight organic peroxide compounds are preferred becausethey are safer and easier to handle and store, as well as being morestable at higher temperatures.

The organic peroxide is present in the grafting reaction in an amountsufficient to effectuate a grafting reaction. Usually, the amount is inthe range of about 0.001 to about 5 parts of organic peroxide per 100parts per polymer (phr), preferably in the range of about 0.001 to about1 phr, and most preferably in the range of about 0.005 to about 0.4 phr.Too much organic peroxide can still initiate the grafting reaction, butpolymer degradation, such as vis-breaking of the polymer, can occur. Aconcentration of organic peroxide which is too low does not initiate thegrafting reaction.

The grafting reaction must occur in the polymer melt. Thus, thetemperature of the reaction is in the range from about the polymermelting point to about the polymer decomposition temperature.Preferably, the reaction temperature is in the range from about 20° C.above the polymer melting point to about the decomposition temperatureof the polymer. Most preferably, the lower end of the temperature rangeis utilized to minimize any thermal degradation effects to the polymer.

The time required for the grafting reaction is a length sufficient forthe grafting to occur. Usually, the time is in the range of about 10seconds to about 30 hours, preferably in the range of from about 15seconds to about 3 hours. Most preferably, the reaction time is in therange of from about 30 seconds to about 10 minutes. Shorter times, suchas less than 5 minutes, are preferred to minimize thermal degradationeffects to the polymer.

The grafting reaction can be carried out by either batch or continuousprocesses, provided that all components are well dispersed and wellblended. A continuous process is preferred for ease of operation. Oneexample of a continuous process is to add the polymer(s), stabilizer(s),grafting compound(s), and free radical generator(s) to an extruder. Theorder of addition of the components is not critical. For example, allcomponents can be dry mixed and then extruded. If preferred, thereactants can be added sequentially wherein, for example, the graftingreaction occurs first, and additional stabilizer(s) is added downstreamfrom the extruder.

Reinforcement Materials

The glass fiber reinforcement improves the properties, such as, forexample, the mechanical and thermal properties, of the polymer. Glassreinforcements having a variety of compositions, filament diameters andforms are useful in this invention.

The diameter of the glass fiber is preferably less than 20 micrometers(μm), but may vary from about 3 to about 30 μm. Glass fiber diametersare usually given a letter designation between A and Z. The most commondiameters used in glass reinforced thermoplastics are G-filament (about9 μm) and K-filament (about 13 μm). Several forms of glass fiberproducts can be used for reinforcing thermoplastics. These include yarn,woven fabrics, continuous roving, chopped strand, mats, etc. Continuousfilament strands are generally cut into lengths of 1/8, 3/16, 1/4, 1/2,3/4, and 1 inch or longer for compounding efficacy in various processesand products.

Any fiberous silicon oxide material can be used. Examples of types ofglass include, but are not limited to, type A glass (an alkali glass),type E glass (a boroaluminosilicate), type C glass (a calciumaluminosilicate), and type S glass (a high-strength glass). Type E glassis presently preferred due to economic reasons and commercialavailability.

Commercial glasses sold for use as reinforcement material inthermoplastics are usually sized during either the fiber formationprocess or in a posttreatment, and thus are sold with sizing materialsalready incorporated.

The amount of sizing on the glass fiber product typically ranges fromabout 0.2 to about 1.5 weight percent based on total weight of the glassand the sizing, although loadings up to 10 percent may be added to matproducts.

Depending upon what thermoplastic is to be used, the intendedapplications, and variations in glass processed by differentmanufacturers even for the same intended end uses, there are differencesin the sizing compositions. The compositions are usually proprietary andmany are not disclosed by the manufacturers.

The sizing compositions usually contain a lubricant, which providesprotection for the glass fiber strand; a film-former or binder whichgives the glass strand integrity and workability; and a coupling agentwhich provides better adhesion between the glass fiber strand and thepolymeric materials that are being reinforced with the glass fiberstrand. The lubricant, film-former, and coupling agent can be a singlecompound or a mixture of two or more compounds. Additional agents whichmay be used in sizing compositions include emulsifiers, wetting agents,nucleating agents, and the like.

The film-former is usually water soluble or water emulsifiable duringprocessing and must be non-sensitive to water after curing. Examples offilm-formers include, but are not limited to, polyesters, epoxy resins,polyurethanes, polyacrylates, polyvinyl acetates, polyvinyl alcohols,styrene-butadiene latexes, starches, and the like.

The coupling agent is usually a silane coupling agent that has ahydrolyzable moiety for bonding to the glass and a reactive organicmoiety that is compatible with the polymeric material which is to bereinforced with the glass fibers.

The sizing compositions for use in this invention include those whichhave as an ingredient: (a) one or more epoxy-functional silanes as acoupling agent or, (b) one or more polyfunctional epoxy resins as afilm-former or, (c) a mixture of one or more epoxy-functional silanesand one or more polyfunctional epoxy resins. One such glass fiberreinforcement is produced by CertainTeed Corporation of Valley Forge,Pa., and marketed under the trade designation of Chopped Strand 930,K-filament glass fibers. This glass is marketed for use in polybutyleneterephthalate, polycarbonate and styrenic resin systems. Another glassfiber reinforcement which is suitable for use in this invention is thatmanufactured by PPG Industries, Inc., of Pittsburgh, Pa., and marketedunder the trade designation Type 1156 Chopped Strand, G-filament glassfibers. PPG Type 1156 glass is marketed for use in thermoset resinsystems such as phenolic, epoxy, DAP (diallyl phthalate), and thermosetpolyesters. Alternatively, commercially sized glass without one or moreof these ingredients can be used for this invention if (a) one or moreepoxy-functional silanes or, (b) one or more polyfunctional epoxy resinsor, (c) a mixture of one or more epoxy-functional silanes and one ormore polyfunctional epoxy resins is blended with the polymer prior tografting, and/or added to the polymer melt during the grafting, and/oradded during reprocessing of the grained, glass reinforced polymer.

Epoxy-functional silanes and polyfunctional epoxy resins contemplated asuseful in this invention are described in greater detail in the next twosections. The epoxy resins may also provide the hydroxy functionality ofthose embodiments of this invention which call for use ofhydroxy-functional compounds.

The glass fiber reinforcement should be present in the range of about 10to about 200 parts by weight glass fiber per hundred parts by weight ofpolymer (phr). Preferably, the glass fibers are present in the range ofabout 10 to about 120 phr, and most preferably in the range of about 10to about 80 phr. Expressed in other terms, the glass fibers should bepresent in about 10 to about 67 weight percent, based on the weight ofthe total product. Preferably, the glass fibers are present in the rangeof about 10 to about 55 weight percent, and more preferably in the rangeof about 10 to about 45 weight percent. Using too small an amount ofglass fiber does not improve the polymer properties. Having too muchglass fiber results in not enough polymer to coat the glass fibers;i.e., the fibers are not "wetted out."

The glass fibers can be added any time during processing after thepolymer has been initially stabilized with the hindered phenolprophylactic charge. Batch or continuous processes can be used, as longas all components are well dispersed and well blended. A continuousprocess is presently preferred for ease of operation. One example of acontinuous process is to add the polymer, stabilizer(s), graftingcompound(s), free radical generator(s), commercially available glassfibers, and optionally, polyfunctional epoxy resin(s) and/orepoxy-functional silane(s) and/or hydroxy-functional resins to anextruder. As with the grafting reaction process, the components can beadded in any order. For example, all components can be dry mixed andthen extruded. If preferred, the reactants can be added sequentially;for example, the grafting reaction occurs first within the presence ofthe polyfunctional epoxy resin(s) and/or epoxy-functional silane(s)and/or hydroxy-functional resins, and additional stabilizer(s) and thenglass fibers are added downstream in the extruder after the graftingreaction has taken place. This latter example is the presently preferredprocess.

Epoxy-functional Silanes

The epoxysilanes contemplated as useful in making the compositions ofthis invention include epoxysilanes within the formula: ##STR1## whereinZ is ##STR2## X is a linear or branched alkylene, arylene orarylalkylene hydrocarbon radical having from 1 to about 15 carbon atoms;

R₁ is a hydrocarbon radical having from 1 to about 8 carbon atoms;

R is (a) a hydrocarbon radical having from 1 to about 8 carbon atoms, or(b) a chlorine atom;

m is an integer of at least 1; and

n is an integer of 1 to 3.

The two different R. groups will not necessarily be the same. Presentlypreferred are epoxysilanes within the formula above wherein n is equalto 3.

Examples of particularly suitable epoxy-functional silanes are3-glycidoxypropyltrimethoxysilane,3-glycidoxypropyldimethylethoxysilane;2-(3,4-epoxy-4-methylcyclohexyl)propyl!methyldiethoxysilanebeta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,3-glycidoxypropylmethyldiethoxysilane, 2-glycidoxypropyltrimethoxysilaneand mixtures of the foregoing epoxy-functional silanes. The presentlymost preferred epoxy-functional silanes are3-glycidoxypropyltrimethoxysilane which is commercially available fromthe Union Carbide Corporation under the trade designation A-187, andbeta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, which is available fromthe Union Carbide Corporation under the trade designation A-186.

A technical/modified grade of 3-glycidoxypropyltrimethoxysilane iscommercially available from Union Carbide Corporation under the tradedesignation Ucarsil™ TC-100 organosilicon chemical.

One or more of the epoxy-functional silanes is present in an amountsufficient to effectuate a desired change in the properties of articlesmade from the glass reinforced polymer. When the epoxy-functionalsilanes are added to the polymer, this amount is generally in the rangeof about 0.05 to about 5 parts by weight epoxy-functional silane perhundred parts polymer (phr), more preferably, in an amount in the rangeof about 0.2 to about 1.6 phr and, most preferably, in an amount ofabout 0.4 to about 1.2 phr. When the epoxy-functional silanes arecomponents of the sizing on the glass, this amount is generally in therange of about 0.05 to about 0.5 weight percent based on total weight ofthe glass and sizing on the glass.

If too much epoxy-functional silane is used, no appreciable polymerproperty improvement is obtained; an excess is economically undesirable.Use of too little epoxy-functional silane does not improve or enhancethe polymer properties.

Epoxy Resins

The term epoxy resin refers to materials which contain an epoxy oroxirane group. Polyfunctional epoxy resins contemplated as useful inthis invention are compounds having two or more epoxy groups in themolecule. The most common commercial epoxy resins are based on combiningbisphenol A and excess epichlorohydrin to form liquid polymers withepoxy end-groups. Liquid epoxy resins can be further reacted withbisphenol A by chain extension to form solid resins of higher molecularweight. Other intermediate-molecular-weight epoxy resins can be preparedby chain extension of liquid epoxy resins and brominated bisphenol A.Epoxy resins are also based on aliphatic backbone structures, such as,for example polyglycidyl ethers of 1,4-butanediol, neopentyl glycol,trimethylolpropane, or higher functionality polyols. Other prominenttypes of epoxy resins include the multifunctional epoxy phenol andcresol novalacs, which are based on phenol or cresol and formaldehydeand subsequent epoxidation with epichlorohydrin. Examples ofpolyfunctional epoxy resins include, but are not limited to, bisphenol Aepoxy compounds, bisphenol F epoxy compounds, aliphatic ether epoxycompounds, novalac epoxides, isocyanurate epoxides, and mixturesthereof. Specific examples of these include condensates betweenbisphenol A and epichlorohydrin; polyglycidol ethers of polyols such asethylene glycol, propylene glycol, polyethylene glycol, glycerol,neopentyl glycol, trimethylol propane, and sorbitol; triglycidylisocyanurate, N-methyl-N',N"-diglycidyl isocyanurate, and triglycidylcyanurate. The presently preferred molecular weight of thesepolyfunctional epoxides is about 4,000 or or less, though the molecularweight could be higher.

The presently most preferred polyfunctional epoxy resin is a highsoftening point (solid) condensation product of bisphenol A andepichlorohydrin.

One or more of the epoxy resins is present in an amount sufficient toeffectuate a desired change in the properties of articles made from theglass reinforced polymers. When the epoxy resin is added to the polymer,this amount is generally in the range of about 0.05 to about 5 parts byweight epoxy resin per hundred parts polymer (phr), more preferably, inan amount in the range of about 0.1 to about 5 phr and, most preferably,in an amount of about 0.1 to about 2.5 phr. When the epoxy resin is acomponent of the sizing on the glass, this amount is generally in therange of about 0.15 to about 2 weight percent based on total weight ofthe glass and the sizing.

If too much epoxy resin is used, no appreciable polymer propertyimprovement is obtained; an excess is economically undesirable. Use oftoo little epoxy resin does not improve or enhance the polymerproperties.

Hydroxy-Functional Compounds

Polymeric or oligomeric hydroxy-functional compounds can be used in thecompositions of this invention to further improve properties of articlesmade from the compositions. Addition of appropriate amountshydroxy-functional compounds to the mixture of stabilized graftedbranched higher alpha-olefin polymer, reinforcing materials and otheradditives during compounding will result in improved tensile strength,flexural strength, flexural modulus, and Izod impact strength.

The hydroxy-functional compounds useful in this invention can be eithercondensation or addition polymers or oligomers. A degree ofpolymerization of at least 2 is generally necessary and the degree ofpolymerization can be as large as about 100,000. A preferred range ofthe degree of polymerization is from about 5 to about 5000.

A useful category of condensation products includes the reactionproducts of polyhydridic phenols and epihalohydrins. Presently preferredin this category are bisphenols and epihalohydrins with epoxideequivalent weights greater than about 2,000. An example is bisphenol Aand epichlorohydrin where the bisphenol A is combined with an excess ofepichlorohydrin to form liquid or solid polymers with epoxy end-groupsand pendant hydroxyl groups as previously described. Liquid resins andlow equivalent weight solid resin solutions are generally cured throughthe terminal epoxy groups. Intermediate equivalent weight solid epoxyresins are generally cured through both the terminal epoxy groups andthe pendant hydroxyl groups in the polymer backbone. High equivalentweight resins, which can be classified as poly(hydroxy ethers), containlow concentrations of epoxy end-groups and are cured through the pendanthydroxyl groups. Thus the hydroxy-functionality can be supplied by thesame polyfunctional resins which supply the epoxy-functionality in theembodiments of this invention which require an epoxy resin.

High equivalent weight condensation products of bisphenol A andepichlorohydrin are commercially available, for example, from ShellChemical Company as Epon™ 1009F (2,300-3,800 epoxide equivalent weight)or from Ciba-Geigy Corporation as Araldite™ GT7099 (2,500-3,575 epoxideequivalent weight).

Other condensation reactions can be used to form hydroxy functionalcompounds which can be used in this invention. These includeesterification of polyhydroxyl alcohols R₁ --(OH)_(n), n>2!,polycarboxylic acids R₂ --(COOH)_(m), m>2! and hydroxy-functional acids(OH)_(n) --R₃ --(COOH)_(m), n>2, M>2!, wherein R₁, R₂ and R₃ arehydrocarbyl groups. Examples of polyhydroxyl alcohols includetrimethylolpropane, glycerin, pentaerythritol and the like. Examples ofpolycarboxylic acids include maleic acid, fumaric acid, succinic acid,terephthalic acid and the like. Examples of hydroxy-functional acidsinclude dihydroxybenzoic acid, dihydroxy fumaric acid and the like.

Hydroxy-functional addition products contemplated as useful in thisinvention can be formed from hydroxy-functional vinyl unsaturatedmonomers either with or without an unsaturated comonomer. Examples ofhydroxy- functional unsaturated monomers include "vinyl alcohol"hydrolyzed or partially hydrolyzed vinyl acetate polymers or oligomers!,allyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, hydroxypropylacrylate, hydroxypropyl methacrylate, glycerol monoacrylate, glycerolmonomethacrylate, glycerol monoallyl ether, 4-vinyl phenol,trimethylolpropane monoallyl ether, pentaerythritol monoacrylate,pentaerythritol monomethacrylate, etc. Examples of appropriate vinylunsaturated comonomers include ethylene, propylene, styrene,4-methyl1-pentene, acrylic acid, acrylic acid esters, acrylic acidamides, methacrylic acid, methacrylic acid esters, methacrylic acidamides, and C through C or higher α-olefins. Other unsaturatedcomonomers such as norbornene, cyclopentadiene, butadiene, isobutylene,etc., can be used.

One or more of the hydroxy-functional compounds, when used, is presentin an amount sufficient to effectuate a desired change in the propertiesof articles made from the glass reinforced polymers. When thehydroxy-functional compound is added to the branched higher alpha-olefinpolymer, this amount is generally in the range of about 0.05 to about 5parts by weight hydroxy-functional compound per hundred parts polymer(phr), more preferably, in an amount in the range of about 0.1 to about5 phr and, most preferably, in an mount of about 0. 1 to about 2.5 phr.Use of too much of the hydroxy functional compound will result in noappreciable polymer property improvement being obtained; an excess iseconomically undesirable. Use of too little hydroxy-functional compounddoes not improve or enhance the polymer properties.

EXAMPLES

The polymethylpentene (PMP) used in the following examples was ahomopolymer prepared from 4-methyl-1-pentene (4MP1) by conventionalpolymerization processes, such as, for example, according to theprocesses disclosed in U.S. Pat. No. 4,342,854, which is herebyincorporated herein by reference.

The undried polymer was stabilized immediately after polymerization bymixing the polymer with about 0.1% based on total resin of a solution ofa hindered phenolic prophylactic stabilizer, octadecyl3-(3,5-di-tert-tert-butyl-4-hydroxyphenyl)propionate. See U.S. Pat. No.4,888,394, which is hereby incorporated herein by reference. Thesecombined solutions were then dried to remove the liquids and produce atreated, stabilized polymer. The polymer had a nominal melt index ofabout 26 grams/10 minutes. The melt index was measured according to ASTMMethod D1238 using a 5 kilogram weight at 260° C.

In each of the following Examples I through VI, 100 parts of treated,stabilized polymer were mixed with 0.04 phr zinc stearate, 0.25 phrtetrakis(methylene3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)methane (availablecommercially from Ciba-Geigy Corporation as Irganox ®1010), 0.50 phr3-methacryloxypropyltrimethoxysilane (available from Union CarbideCorporation as A-174 organofunctional silane), and 0.10 phr2,5-dimethyl-2,5-(di-tert-butylperoxy)hexane (available from CatalystResources, Inc., as Aztec 2,5-Di). The components were dry mixed forabout 60 minutes at about 25° C. (room temperature) by drum tumbling.

In each of the following Examples VII through XI, the same procedure forpreparing, stabilizing and grafting the polymer was used, with theexception that 0.80 phr of maleic anhydride was used in place of the3-methacryloxypropyltrimethoxysilane.

In the following example XII, a similar procedure for preparing,stabilizing and grafting the polymer was used, with the exception that0.50 phr of muconic acid was used in place of the3-methacryloxypropyltrimethoxysilane.

EXAMPLE I

Compound 1 is a silane grafted control example for comparison purposes.The drum tumbled polymer mixture described above was mixed by hand with43.24 parts glass fiber reinforcement in a plastic bag (bag mixed) toproduce a mixture with 30 weight percent glass fiber reinforcement. Theglass reinforcement product used was a commercially available productsized for compatibility with polypropylene produced by Owens-CorningFiberglas Corporation and designated 457BA. This product was alsorecommended by the manufacturer as appropriate for use in reinforcingstereoregular polymers of branched, higher alpha-olefins such as PMP.This glass is a K-filament diameter glass fiber with a 3/16-inch fiberlength. It is believed that the film-former in the sizing compositionfor 457 BA glass fibers is a carboxylic styrene-butadiene latex and thatthe coupling agent is an amino-functional silane(3-aminopropyltriethoxysilane), although the exact composition of thesizing is not disclosed by the manufacturer. It is also believed that457 BA glass fibers contain terephthalic acid as a nucleating agent. Theamount of sizing on the product is about 0.9 weight percent of the totalproduct weight. The mixture was compounded on a Werner & PfleidererZSK-30 twin screw extruder with a general purpose compoundingbarrel/screw configuration. The screw speed was 250 rpm and thetemperature profile was 260°-290° C. Throughput was 20 pounds per hour.The compound was stranded, pelletized and dried overnight at 110° C. Theresulting compound was injection molded into ASTM test specimens using aModel EC88 Engel injection molding machine with a 55-ton clamp force.The mold temperature was set at 93° C. and the barrel temperature at270° to 280° C., ascending from the beginning to the end of the barrel.Cycle time was approximately 30 seconds. Measured properties of testspecimens molded from the resin of Compound 1 are listed in Table III.The following test procedures were utilized to test all of the Compoundsgiven in these examples.

                  TABLE II    ______________________________________    Test Procedure Used    Analysis           ASTM Method No.    ______________________________________    Tensile Strength at Break (psi)                       D638, at 5 mm/min    Elongation at Break (%)                       D638, at 5 mm/min    Flexural Strength (psi)                       D790, 2 inch span, 1 mm/min    Flexural Modulus (ksi)                       D790, 2 inch span, 1 mm/min    Izod Impact Strength, Notched                       D256    and Unnotched (ft-lb/in)    Heat Deflection Temperature (°C.)                       D648, at 264 psi load    ______________________________________

EXAMPLE II

In this inventive example, the glass fiber reinforcement material usedwas not one generally recommended for use with polyolefins but was,instead, one recommended for use with polybutylene terephthalate (athermoplastic polyester), polycarbonate and styrenic resin systems.

The glass fiber reinforcement material used in this example was acommercial product from CertainTeed Corporation designated ChoppedStrand 930. This is a K-filament diameter glass fiber with a 1/8-inchfiber length. It is believed that the sizing composition contains both apolyfunctional epoxy resin film-former and an epoxy-functional silane.It is further believed that the polyfunctional epoxy resin is acondensation product of bisphenol A and epichlorohydrin and that theepoxy-functional silane is 3-glycidoxypropyltrimethoxysilane, althoughthe exact composition of the sizing is not disclosed by themanufacturer. The amount of sizing on the product is about 0.80 weightpercent based on total weight of the sized glass.

The process described above for Example I was repeated with theexception that the glass fiber reinforcement material used was theChopped Strand 930 glass fiber reinforcement material described above.The properties of test specimens molded from the resulting compound(Compound 2) are listed in Table III.

It is clear from the data that glass fiber reinforcement with a sizingcomposition which includes both a polyfunctional epoxy resin and anepoxy-functional silane provides significantly better mechanicalproperties in test specimens molded from compounds of silane grafted,glass reinforced, stereoregular polymers of branched, higheralpha-olefins than glass reinforcements sized for compatibility withpolyolefins such as those described in Example I above.

EXAMPLE III

In this inventive example, the glass fiber reinforcement product usedwas not one generally recommended for use with polyolefins but was,instead, one recommended for use in phenolic, epoxy, DAP (diallylphthalate), and thermoset polyester resin systems. The specific productis a commercial product from PPG Industries, Inc., designated Type 1156Chopped Strand. It is a G-filament diameter glass fiber with a 1/8-inchfiber length. Although the exact sizing composition is not disclosed bythe manufacturer, it is believed that Type 1156 Chopped Strand containsboth a polyfunctional epoxy resin film-former and an epoxy-functionalsilane. The amount of sizing on the product is about 1.15 weight percentbased on total weight of the sized glass.

The process described above for Example I was repeated with theexception that the glass fiber reinforcement product was Type 1156Chopped Strand. The properties of test specimens molded from theresulting compound (Compound 3) are listed in Table III.

It is again clear from the data that glass fiber reinforcement with asizing composition which includes both a polyfunctional epoxy resin andan epoxy-functional silane provides significantly better mechanicalproperties in test specimens molded from compounds of silane grafted,glass reinforced, stereoregular polymers of branched, higheralpha-olefins than glass reinforcements sized for compatibility withpolyolefins such as those described in Example I above. The additionalimprovement in properties of test specimens molded from Compound 3compared to those molded from Compound 2 is due to the smaller filamentdiameter of the glass fiber reinforcement.

EXAMPLE IV

In this inventive example, an epoxy-functional silane,3-glycidoxypropyltrimethoxysilane (Ucarsil™ TC-100 available from UnionCarbide Corporation) was used in conjunction with glass fiber of thetype used in Example I, one sized for compatibility with polypropylene.The procedure was that of Example I, with the epoxy-functional silaneincluded with the group of ingredients which were bag mixed.

    ______________________________________    PMP, vinyl-polymerizable silane and additives                              100.89 parts    epoxy-functional silane   0.50 parts    OCF 457 BA glass fiber    43.45 parts    ______________________________________

The PMP with additives was a drum tumbled mixture as described in theintroduction to these examples. Properties of the resulting compound(Compound 4) are listed in Table III.

The mechanical properties of test specimens molded from Compound 4relative to the properties of those molded from Compound 1 which did nothave an epoxy-functional silane are significantly better.

EXAMPLE V

In this inventive example, a polyfunctional epoxy resin typical of"epoxy film formers" used in some glass fiber reinforcement sizingcompositions was used in conjunction with the glass fiber reinforcementsized for compatibility with polypropylene which was used in Example I.The specific epoxy compound used was a bisphenol A extended bisphenolA/epichlorohydrin condensation product available from Shell ChemicalCompany as Epon™ 1009F. The epoxide equivalent weight is approximately2,300-3,000. The procedure was that of Example I, with thepolyfunctional epoxy resin included with the group of ingredients whichwere bag mixed. The following ingredients were bag mixed:

    ______________________________________    PMP, vinyl-polymerizable silane and additives                              100.89 parts    epoxy-resin (Epon ™ 1009)                              1.00 parts    OCF 457 BA glass fiber    43.67 parts    ______________________________________

The PMP with additives was a drum tumbled mixture as described in theintroduction to these examples. Properties of test specimens molded fromthe resulting compound (Compound 5) are given in Table III.

The mechanical properties of test specimens molded from Compound 5relative to the properties of those molded from Compound 1 which did nothave a polyfunctional epoxy resin are significantly better.

EXAMPLE VI

In this inventive example both the epoxy-functional silane used inExample IV and the epoxy resin used in Example V were used inconjunction with the glass fiber reinforcement sized for compatibilitywith polypropylene used in Example I. Essentially, the procedures ofExamples IV and V were repeated except that the ingredients and theirrelative weight levels were as follows:

    ______________________________________    PMP, vinyl-polymerizable silane and additives                              100.89 parts    epoxy-functional silane   0.50 parts    epoxy resin               1.00 parts    OCF 457 BA glass fiber    43.88 parts    ______________________________________

The PMP with additives was a drum tumbled mixture as described in theintroduction to these examples. The properties of the resulting compound(Compound 6) are listed in Table III.

The increase in properties of Compound 6 relative to those of Compound 1is again apparent.

This example, as well as the inventive Examples II, III, IV and Vdescribed above, indicates that sizing compositions fur treating glassfibers which contain (a) one or more polyfunctional epoxy resins as afilm-former, (b) one or more epoxy-functional silanes as a couplingagent or, (c) a mixture of one or more polyfunctional epoxy resins andone or more epoxy-functional silanes, provide improved adhesion betweenthe glass fiber strand and silane grafted stereoregular polymers ofbranched, higher alpha-olefins.

This example, as well as the proceeding examples described above, alsoindicates that as an alternative commercially sized glass fiber productswithout one or more of these ingredients can be used to provide improvedadhesion between the glass fiber strand and silane grafted stereoregularpolymers of branched higher alpha-olefins if (a) one or morepolyfunctional epoxy resins or, (b) one or more epoxy-functional silanesor, (c) a mixture of one or more polyfunctional epoxy resins and one ormore epoxy-functional silanes is blended with the PMP and additives forsilane grafting described in this invention.

                  TABLE III    ______________________________________    Properties of Glass Reinforced Silane Grafted Branched    Higher Alpha-Olefin Polymers with Epoxy-Functional    Silanes and/or Epoxy Resins            Com-            pound 1  Com-    Com-  Com-  Com-  Com-            (Con-    pound   pound pound pound pound    Properties            trol)    2       3     4     5     6    ______________________________________    Tensile  8,900   11,200  11,700                                   10,100                                          9,800                                               10,300    Strength,    psi    Flexural            12,700   15,400  16,100                                   13,700                                         13,400                                               13,700    Strength,    psi    Flexural              765      855     812   788   780   780    Modulus,    ksi    Elongation,            3.5      4.7     5.0   3.8   3.9   3.9    Notched 1.1      1.4     1.2   1.2   1.1   1.1    Izod    Impact    Strength,    ft-lb/in    Unnotched            3.5      6.5     5.9   4.2   4.4   4.5    Izod    Impact    Strength,    ft-lb/in    Heat      187      188     196   183   185   186    Distortion    Tempera-    ture at 264    psi, °C.    ______________________________________

EXAMPLE VII

Compound 7 is a control example for comparison purposes. The followingcomponents were dry mixed for about 60 minutes at 25° C. (roomtemperature) by drum tumbling.

    ______________________________________    PMP homopolymer        100 parts    zinc stearate          0.04 parts    Irganox 1010           0.25 parts    maleic anhydride       0.80 parts    Aztec 2,5-Di           0.10 parts    ______________________________________

This drum tumbled mixture was then mixed by hand with 43.37 parts glassfiber reinforcement in a plastic bag (bag mixed) to produce a mixturewith 30 weight percent, based on weight of the polymer and additives, ofglass fiber reinforcement. The glass reinforcement product used was acommercially available product sized for compatibility withpolypropylene produced by Owens-Corning Fiberglas Corporation anddesignated 457 BA. This glass product was described in Example I above.The mixture was compounded, stranded, pelletized and dried as describedin Example I. The resulting compound was injection molded into ASTM testspecimens and tested as described in Example I. Measured properties oftest specimens molded from the resin of Compound 7 are listed in TableIV. The test procedures shown in Table II above were utilized to testall of the Compounds given in these examples. EXAMPLE VIII

In this inventive example, the glass fiber reinforcement material usedwas not one generally recommended for use with polyolefins but is,instead, one recommended for use with polybutylene terephthalate (athermoplastic polyester), polycarbonate and styrenic resin systems.

The glass fiber reinforcement material used in this example was acommercial product from CertainTeed Corporation designated ChoppedStrand 930. This glass fiber reinforcement material was described inExample II above.

The process described above for Example VII was repeated with theexception that the glass fiber reinforcement material used was theChopped Strand 930 glass fiber reinforcement material described inExample II. The properties of test specimens molded from the resultingcompound (Compound 8) are listed in Table IV.

It is clear from the data that glass fiber reinforcement with a sizingcomposition which includes both a polyfunctional epoxy resin and anepoxy-functional silane provides significantly better mechanicalproperties in test specimens molded from compounds of maleic anhydridegrafted, glass reinforced, stereoregular polymers of branched, higheralpha-olefins than does use of glass reinforcements sized forcompatibility with polyolefins such as those used in Example VII above.

EXAMPLE IX

In this inventive example, an epoxy-functional silane,3-glycidoxypropyltrimethoxysilane (Ucarsil™ TC-100 available from UnionCarbide Corporation) was used in conjunction with glass fiber of thetype used in Example VII, one sized for compatibility withpolypropylene. The procedure was that of Example VII, with theepoxy-functional silane included with the group of ingredients whichwere bag mixed:

    ______________________________________    PMP, carboxylic anhydride and additives                             101.19 parts    epoxy-functional silane  0.50 parts    OCF 457 BA glass fiber   43.45 parts    ______________________________________

The PMP with additives was a drum tumbled mixture as described in theintroduction to these examples. Properties of the resulting compound(Compound 9) are listed in Table IV.

The increase in mechanical properties of test specimens molded fromCompound 9 relative to the properties in compounds of maleic anhydridegrafted, glass reinforced, stereoregular polymers of branched, higheralpha-olefins such as that of Compound 7 which did not have anepoxy-functional silane is readily apparent.

EXAMPLE X

In this inventive example, a polyfunctional epoxy resin typical of"epoxy film formers" used in some glass fiber reinforcement sizingcompositions was used in conjunction with the glass fiber reinforcementsized for compatibility with polypropylene which was used in ExampleVII. The specific epoxy compound used was a bisphenol A extendedbisphenol A/epichlorohydrin condensation product available from ShellChemical Company as Epon™ 1009F. The epoxide equivalent weight isapproximately 2,500-4,000. The procedure was that of Example VII, withthe polyfunctional epoxy resin included with the group of ingredientswhich were bag mixed. The ingredients which were bag mixed were asfollows:

    ______________________________________    PMP, carboxylic anhydride and additives                             101.19 parts    epoxy resin              1.00 parts    OCF 457 BA glass fiber   43.67 parts    ______________________________________

The PMP with additives was a drum tumbled mixture as described in theintroduction to these examples.

Properties of test specimens molded from the resulting compound(Compound 10) are given in Table IV.

The increase in mechanical properties of test specimens molded fromCompound 10 relative to the properties of test specimens molded fromCompound 7 which did not have a polyfunctional epoxy resin is readilyapparent.

EXAMPLE XI

In this inventive example both the epoxy-functional silane used inExample IX and the epoxy resin used in Example X were used inconjunction with the glass fiber reinforcement sized for compatibilitywith polypropylene used in Example VII. Essentially, the procedures ofExamples IX and X were repeated except that the ingredients were asfollows:

    ______________________________________    PMP, carboxylic anhydride and additives                             101.19 parts    epoxy-functional silane  0.50 parts    epoxy resin              1.00 parts    OCF 457 BA glass fiber   43.88 parts    ______________________________________

The PMP with additives was a drum tumbled mixture as described in theintroduction to these examples.

The properties of test specimens molded from the resulting compound(Compound 11) are listed in Table IV.

The increase in properties of test specimens molded from Compound 11relative to those of Compound 7 is again apparent.

This example, as well as the inventive Examples VIII, IX and X describedabove, indicates that sizing compositions for treating glass fiberswhich contain (a) one or more polyfunctional epoxy resins as afilm-former, (b) one or more epoxy-functional silanes as a couplingagent or, (c) a mixture of one or more polyfunctional epoxy resins andone or more epoxy-functional silanes, provide improved adhesion betweenthe glass fiber strand and maleic anhydride grafted stereoregularpolymers of branched, higher alpha-olefins.

This example, as well as the preceding examples described above, alsoindicates that as an alternative commercially sized glass fiber productswithout one or more of these ingredients can be used to provide improvedadhesion between the glass fiber strand and maleic anhydride graftedstereoregular polymers of branched higher alpha-olefins if (a) one ormore polyfunctional epoxy resins or, (b) one or more epoxy-functionalsilanes or, (c) a mixture of one or more polyfunctional epoxy resins andone or more epoxy-functional silanes is blended with the PMP andadditives for maleic anhydride grafting described in this invention.

                                      TABLE IV    __________________________________________________________________________    Properties of Glass Reinforced Carboxylic Anhydride Grafted Branched    Higher    Alpha-Olefin Polymers with Epoxy-Functional Silanes and/or Epoxy Resins                    Compound 7                           Compound                                 Compound                                       Compound                                             Compound    Properties      (Control)                           8     9     10    11    __________________________________________________________________________    Tensile Strength, psi                    7,800  11,300                                 10,700                                       9,800 10,500    Flexural Strength, psi                    10,700 16,300                                 15,700                                       14,100                                             15,300    Flexural Modulus, ksi                    741    779   784   746   792    Elongation, %   2.7    5.0   4.8   4.2   4.3    Notched Izod Impact Strength,                    0.8    1.9   1.6   1.2   1.5    ft-lb/in    Unnotched Izod Impact Strength,                    3.2    10.3  9.5   6.0   7.2    ft-lb/in    Heat Distortion Temperature                    162    195   194   189   189    at 264 psi, °C.    __________________________________________________________________________

EXAMPLE XII

In this inventive example, the glass fiber reinforcement material usedwas not one generally recommended for use with polyolefins but is,instead, one recommended for use with polybutylene terephthalate (athermoplastic polyester), polycarbonate and styrenic resin systems.

The glass fiber reinforcement material used in this example was acommercial product from CertainTeed Corporation designated ChoppedStrand 930. This glass fiber reinforcement material was described inExample II above.

The process similar to that described above for Example VII was repeatedwith the exceptions that: (a) the glass fiber reinforcement materialused was the Chopped Strand 930 glass fiber reinforcement materialdescribed in Example II; and (b) the PMP was modified with muconic acidinstead of 3-methacryloxypropyltrimethoxysilane. The PMP, after beingstabilized with a hindered phenol as described in the introduction tothese examples, was mixed with 0.04 phr zinc stearate, 0.10 phrtetrakis(methylene3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)methane (availablecommercially from Ciba-Geigy Corporation as Irganox 1010), 0.50 phrmuconic acid in the form of cis,cis 2,4-hexadienedioic add (availablecommercially from Celgene Corporation) and 0.05 phra,a'-bis(tert-butylperoxy)diisopropyl benzene (available from Hercules,Inc., as Vulcup R). The components were dry mixed for about 60 minutesat about 25° C. (room temperature) by drum tumbling.

The drum tumbled polymer mixture described above was grained using theprocessing conditions as described in Example I and subsequently mixedwith 43.24 parts glass fiber reinforcement in the extruder to produce amixture with 30 weight percent glass fiber reinforcement.

Articles made from the compound produced in this Example XII (Compound12) were tested using the same test methods as were used in all theforegoing examples. The resulting properties shown in the followingTable V indicated that articles made from PMP which had been graftedwith muconic acid and reinforced With glass having sizing containingmaterials with epoxy functionality also demonstrated improved propertieswhen compared with articles made from PMP which had been grafted withunsaturated hydrolyzable silane or carboxylic anhydride and reinforcedwith the same glass reinforcement.

                  TABLE V    ______________________________________    Properties of Glass-Reinforced Muconic Acid Grafted Branched    Higher Alpha-Olefin Polymers with Epoxy-Functional    Silanes and/or Epoxy Resins                   Compound  Compound  Compound    Properties     2.sup.a   8.sup.a   12.sup.b    ______________________________________    Tensile Strength, psi                   11,200    11,300    10,700    Elongation, %  4.7       5.0       5.1    Notched Izod Impact                   1.4       1.9       1.2    Strength, ft-lb/in    Unnotched Izod Impact                   6.5       10.3      6.1    Strength, ft-lb/in    Heat Distortion                   188       195       199    Temperature at 264°    psi, °C.    ______________________________________     .sup.a Runs 2 and 8 are repeated here for purposes of easier comparison.     Compound 2 was made using PMP grafted with an unsaturated hydrolyzable     silane. Compound 8 was made using PMP grafted with a carboxylic acid.     .sup.b Compound 12 was made using PMP grafted with muconic acid.

EXAMPLE XIII

This example demonstrates the efficacy of using resins with hydroxyfunctionality in glass reinforced silane grafted polymethylpentenemolding compounds. This is particularly useful when using glassreinforcing materials which have sizing containing: (a) one or morepolyfunctional epoxy resins as a film-former, (b) one or moreepoxy-functional silanes as a coupling agent or, (c) a mixture of one ormore polyfunctional epoxy resins and one or more epoxy functionalsilanes.

The polymethylpentene (PMP) used in Examples XIII, XIV and XV was ahomopolymer fluff prepared and stabilized as described in theintroduction to these examples. PMP with a melt flow of 12.7 g/10 minwas used in this Example XIII.

In this inventive example, a high epoxide equivalent weight epoxy resinswas used in conjunction with glass fiber of the type used in ExampleIII, one sized for compatibility with phenolic, epoxy, DAP (diallylphthalate), and thermoset polyester resin systems. The specifichydroxy-functional compound used in this example was a bisphenol Aextended bisphenol A/epichlorohydrin condensation product available fromShell Chemical Company as Epon™ 1009F. The epoxide equivalent weight ofthis epoxy resin was approximately 2,300-3,800. This epoxy resin has ahigh concentration of pendant hydroxy groups relative to theconcentration of the epoxy end-groups. The hydroxy/epoxy ratio of Epon™1009F resin is approximately 9:1. According to the product literaturethe hydroxy content of this resin is approximately 0.32-0.34 equivalentsper 100 grams.

The procedure was that of Example I, with the hydroxy-functionalcompound included with the group of ingredients which were bag mixed.The hydroxy-functional resin was ground in a Thomas mill to facilitateblending.

The following ingredients were mixed by hand in plastic bags to producemixtures with 30% by weight glass reinforcement:

    ______________________________________    PMP, vinyl-polymerizable silane and additives                               100.89 parts    Epon ™ 1009F epoxy resin                               1.00 parts    PPG Type 1156 glass fiber  43.67 parts    ______________________________________

The PMP with additives was a drum tumbled mixture as described in theintroduction to these examples.

The mixture was compounded (designated compound 13) and molded into testspecimens as described in previous examples. The properties of the testspecimens were determined using ASTM methods indicated in Table IIabove. Properties of test specimens molded from the resultant compound(Compound 13) are given in Table VI.

The mechanical properties of test specimens molded from Compound 13 werecompared to the properties of those molded from inventive Compound 3which did not have a hydroxy-functional additive and which wasreinforced with the same type of glass fiber having the same sizingmaterials. This comparison of properties showing improvementattributable to use of the hydroxy-functional additive is presented inTable VI.

                                      TABLE VI    __________________________________________________________________________    Effect of Hydroxy-Functional Additives on Properties of Test Specimens    of    Silane Grafted, 30% Glass Reinforced Polymethylpentene Compounds                         Compound 3.sup.a                                Compound 13.sup.b                                        Compound 14.sup.c                                                Compound 15.sup.d    __________________________________________________________________________    Hydroxy-functional Additive                         None   Epon ™ 1009F                                        poly(styrene-                                                poly(ethylene-                                epoxy resin                                        allyl alcohol)                                                vinyl alcohol)                                                copolymer    Tensile Strength, psi                         11,700 12,500  12,200  12,900    Flexural Strength, psi                         16,100 17,200  17,200  18,600    Flexural Modulus, ksi                         812    787     839     814    Notched Izod Impact Strength, ft-lb/in                         1.2    1.6     1.4     2.1    Unnotched Izod Impact Strength, ft-lb/in                         5.9    8.6     7.1     10.7    Heat Distortion Temperature at 264 psi, °C.                         196    192     192     196    __________________________________________________________________________     .sup.a Inventive Compound 3 of Example III is repeated here for purposes     of easier comparison.     .sup.b Prepared according to Example XIII.     .sup.c Prepared according to Example XIV.     .sup.d Prepared according to Example XV.

EXAMPLE XIV

This example demonstrates use of an addition product of styrene andallyl alcohol to provide hydroxy functionality and the effect of thisadditive on properties of articles made from silane grafted, glassreinforced branched higher alpha-olefin polymers. The polymethylpenteneused in this example was prepared, stabilized, grafted, and compoundedwith glass and additives as described in Example XIII. The PMP had amelt flow of 12.7 g/10 min. The glass fiber used in this example was thesame as that used in Example III, i.e., one sized for use in phenolic,epoxy, DAP (diallyl phthalate), and thermoset polyester resin systems.The poly(styrene-allyl alcohol) was obtained from Polysciences, Inc.,and had a 1500 molecular weight and a 9.7% hydroxyl content(approximately 0.57 equivalents per 100 grams).

The procedure described in Example I for combining the ingredients wasused, with the addition of the hydroxy-functional compound to theingredients which mixed by hand in a plastic bag. The hydroxy-functionalresin was ground in a Thomas mill to facilitate blending.

    ______________________________________    PMP, vinyl-polymerizable silane and additives                               100.89 parts    poly(styrene-allyl alcohol)                               1.00 parts    PPG Type 1156 glass fiber  43.67 parts    ______________________________________

The PMP with additives was a drum tumbled mixture as described in theintroduction to these examples. The mixture was compounded (designatedCompound 14) and molded into test specimens as described in previousexamples. The properties of the test specimens were determined usingASTM methods indicated in Table II above. Properties of test specimensmolded from the resultant compound (Compound 14) are given in Table VI.

The mechanical properties of test specimens molded from Compound 14 werecompared to the properties of those molded from inventive Compound 3which did not have a hydroxy-functional additive and which wasreinforced with the same type of glass fiber having the same sizingmaterials. This comparison of properties showing improvementattributable to use of the hydroxy-functional additive is presented inTable VI.

EXAMPLE XV

This example demonstrates the use of an addition product of ethylene and"vinyl alcohol" to provide hydroxy functionality and the effect of thisadditive on properties of articles made from silane grafted, glassreinforced branched higher alpha-olefin polymers. The polymethylpenteneused in this example was prepared, stabilized, grafted, and compoundedwith glass and additives as described in Example XIII. The PMP had amelt flow of 12.7 g/10 min. The glass fiber used in this example was thesame as that used in Example III, i.e., one sized for use in phenolic,epoxy, DAP (diallyl phthalate), and thermoset polyester resin systems.The poly(ethylene-vinyl alcohol) copolymer was obtained fromPolysciences, Inc. The poly(ethylene-vinyl alcohol) resin was 56% vinylalcohol with approximately 21.6% hydroxyl content (approximately 1.27equivalents per 100 grams).

The procedures described in Example I for combining the ingredients wereused, with the addition of the hydroxy-functional compound to theingredients which mixed by hand in a plastic bag. The hydroxy-functionalresin was ground in a Thomas mill to facilitate blending. The followingingredients were bag mixed:

    ______________________________________    PMP, vinyl-polymerizable silane and additives                               100.89 parts    poly(ethylene-vinyl alcohol) copolymer                               1.00 parts    PPG Type 1156 glass fiber  43.67 parts    ______________________________________

The PMP with additives was a drum tumbled mixture as described in theintroduction to these examples. The mixture was compounded (designatedCompound 15) and molded into test specimens as described in previousexamples. The properties of the test specimens were determined usingASTM methods indicated in Table II above. Properties of test specimensmolded from the resultant compound (Compound 15) are given in Table VI.

The mechanical properties of test specimens molded from Compound 15 werecompared to the properties of those molded from inventive Compound 3which did not have a hydroxy-functional additive and which wasreinforced with the same type of glass fiber having the same sizingmaterials. This comparison of properties showing improvementattributable to use of the hydroxy-functional additive is presented inTable VI.

In general, the results of testing of specimens made from compounds 13,and 15 (shown in Table VI) demonstrate that the use ofhydroxy-functional additives in silane grafted, glass reinforced PMPpolymers surprisingly improves properties.

While the polymers and methods of this invention have been described indetail for the purpose of illustration, the inventive polymers andmethods are not to be construed as limited thereby. This patent isintended to cover all changes and modifications within the spirit andscope thereof.

That which is claimed:
 1. A composition comprising:(a) a stereoregularpolymer of a branched alpha-olefin containing 4-12 carbon atoms permolecule which has been stabilized with at least one hindered phenol;(b) a grafting compound selected from the group consisting ofvinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylicacids; carboxylic acid derivatives: carboxylic acid anhydrides:carboxylic acid anhydride derivatives; and mixtures thereof: (c) a freeradical generator; (d) glass; and (e) at least one hydroxy-functionalcompound selected from the group consisting of poly(hydroxyethers);condensation polymerization products formed from polyhydroxy alcohols,polycarboxylic acids and hydroxy-functional acids; and additionpolymerization products formed from hydroxy-functional vinyl unsaturatedmonomers.
 2. A composition in accordance with claim 1, wherein said atleast one hydroxy-functional compound has a degree of polymerization ofabout 5 to about
 5000. 3. A composition in accordance with claim 1,wherein said stereoregular polymer of a branched alpha-olefin is apolymer of a monomer selected from the group consisting of3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene,4-methyl-1-hexene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-hexene,3-ethyl-1-hexene and mixtures thereof.
 4. A composition in accordancewith claim 3, wherein said stereoregular polymer of a branchedalpha-olefin is a polymer of 3-methyl-1-butene.
 5. A composition inaccordance with claim 3, wherein said stereoregular polymer of abranched alpha-olefin is a polymer of 4-methyl-1-pentene.
 6. Acomposition in accordance with claim 3, wherein said grafting compoundis a vinyl-polymerizable, unsaturated, hydrolyzable silane selected fromthe group consisting of vinyltrichlorosilane, vinyltriethoxysilane,vinyltrimethoxysilane, vinyltris(beta-methoxyethoxy)silane,vinyltriacetoxysilane,3-methacryloxypropyl-trimethoxysilane,3-methacryloxypropyltris(beta-methoxyethoxy)silane, and mixturesthereof; andwherein said free radical generator is selected from thegroup consisting of alkyl peroxides, aryl peroxides, acyl peroxides,aroyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylatesand hydroperoxides.
 7. A composition in accordance with claim 3, whereinsaid stereoregular polymer of a branched, alpha-olefin is a polymer of4-methyl-1-pentene;wherein said grafting compound is avinyl-polymerizable, unsaturated, hydrolyzable silane selected from thegroup consisting of vinyltrichlorosilane,vinyltriethoxysilane,vinyltrimethoxysilane,vinyltris(beta-methoxyethoxy)silane, vinyltriacetoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropyltris(beta-methoxyethoxy)silane, and mixturesthereof; wherein said free radical generator is selected from the groupconsisting of dicumyl peroxide, di-tert-butyl peroxide,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3;a,a'-bis(tert-butylperoxy)diisopropylbenzene, and mixtures thereof; andwherein said hydroxy-functional compound is poly(styrene-allyl alcohol).8. A composition in accordance with claim 3, wherein said stereoregularpolymer of a branched alpha-olefin is a polymer of4-methyl-1-pentene;wherein said grafting compound is avinyl-polymerizable, unsaturated, hydrolyzable silane selected from thegroup consisting of vinyltrichlorosilane,vinyltriethoxysilane,vinyltrimethoxysilane,vinyltris(beta-methoxyethoxy)silane, vinyltriacetoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropyltris(beta-methoxyethoxy)silane, and mixturesthereof; wherein said free radical generator is selected from the groupconsisting of dicumyl peroxide, di-tert-butyl peroxide,2,5-dimethyl-2,5-di(tert-butylperoxide)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3;a,a'-bis(tert-butylperoxy)diisopropylbenzene, and mixtures thereof; andwherein said hydroxy-functional compound is poly(ethylene-vinylalcohol).
 9. A composition in accordance with claim 3, wherein saidgrafting compound is selected from the group consisting of carboxylicacids, carboxylic anhydrides, carboxylic acid derivatives and carboxylicacid anhydride derivatives, and mixtures thereof; andwherein said freeradical generator is selected from the group of alkyl peroxides, arylperoxides, acyl peroxides, aroyl peroxides, ketone peroxides,peroxycarbonates, peroxycarboxylates and hydroperoxides.
 10. Acomposition in accordance with claim 9, wherein said grafting compoundis selected from the group consisting of maleic anhydride and muconicacid.
 11. A composition as recited in claim 9 wherein said stereoregularpolymer of a branched alpha-olefin is a polymer of4-methyl-1-pentene;wherein said grafting compound is an unsaturatedselected from the group consisting of unsaturated carboxylic acids andunsaturated carboxylic anhydrides; wherein said free radical generatoris selected from the group consisting of dicumyl peroxide, di-tert-butylperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy)hexyne-3,a,a'-bis(tert-butylperoxy)diisopropylbenzene, and mixtures thereof; andwherein said hydroxy-functional compound is poly(styrene-allyl alcohol).12. A composition in accordance with claim 9, wherein said stereoregularpolymer of a branched alpha-olefin is a polymer of4-methyl-1-pentene;wherein said grafting compound is selected from thegroup consisting of unsaturated carboxylic acids and unsaturatedcarboxylic anhydrides; wherein said free radical generator is selectedfrom the group consisting of dicumyl peroxide, di-tert-butyl peroxide,2,5-dimethyl-2,5-di(tert-butyl)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3;a,a'-bis(tert-butylperoxy)diisopropylbenzene, and mixtures thereof; andwherein said hydroxy-functional compound is poly(ethylene-vinylalcohol).
 13. A composition in accordance with claim 1, furthercomprising an epoxy resin which consists essentially of a condensationproduct of bisphenol A and epichlorohydrin.
 14. An article ofmanufacture prepared from the composition of claim
 2. 15. An article ofmanufacture prepared from the composition of claim
 1. 16. An article ofmanufacture prepared from the composition of claim
 5. 17. A compositionin accordance with claim 13, wherein said stereoregular polymer of abranched alpha-olefin is a polymer of a monomer selected from the groupconsisting of 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene,4-methyl-1-hexene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-hexene,3-ethyl-1-hexene and mixtures thereof.
 18. Composition in accordancewith claim 17, wherein said stereoregular polymer of a branchedalpha-olefin is 4-methyl-1-pentene, and said at least onehydroxy-functional compound is selected from the group consisting ofpoly(styrene-allyl) alcohol and poly(ethylene-vinyl alcohol).
 19. Anarticle of manufacture prepared from the composition of claim 13.